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(12) United States Patent (10) Patent No.: US 7,557,177 B2 Fansler Et Al

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(12) United States Patent (10) Patent No.: US 7,557,177 B2 Fansler Et Al US00755.71 77B2 (12) United States Patent (10) Patent No.: US 7,557,177 B2 Fansler et al. (45) Date of Patent: Jul. 7, 2009 (54) RING-OPENED AZLACTONE INITIATORS 6,747,104 B1 6/2004 Wendland et al. FORATOM TRANSFER RADICAL 6,753,391 B1 6/2004 Lewandowski et al. POLYMERIZATION 6,762.257 B1 7/2004 Lewandowski et al. 6,784,264 B2 * 8/2004 Lewandowski et al. ..... 526.204 (75) Inventors: Duane D. Fansler, Dresser, WI (US); 6,784,265 B2 8/2004 Fansler et al. Kevin M. Lewandowski, Inver Grove 6,818,716 B2 11/2004 Wendland et al. Heights, MN (US); Babu N. Gaddam, 6,841,637 B2 1/2005 Lewandowski et al. Woodbury, MN (US); Steven M. 6,894,133 B2 5/2005 Lewandowski et al. Heilmann, Afton, MN (US); Larry R. 6,908,952 B2 6/2005 Lewandowski et al. Krepski, White Bear Lake, MN (US); 6,911,510 B2 6/2005 Lewandowski et al. Stephen B. Roscoe, Saint Paul, MN 6,969,749 B2 11/2005 Lewandowski et al. (US); Michael S. Wendland, North 6,992,217 B2 * 1/2006 Fansler et al. ............... 562 567 Saint Paul, MN (US) 7,041,755 B2 5/2006 Lewandowski et al. 2004/0116633 A1 6/2004 Fansler et al. (73) Assignee: 3M Innovative Properties Company, 2004/O152852 A1 8/2004 Lewandowski et al. St. Paul, MN (US) 2004/0152853 A1 8/2004 Fansler et al. 2004/O198933 A1 10, 2004 Wendland et al. (*) Notice: Subject to any disclaimer, the term of this 2004/0225.090 A1 11/2004 Lewandowski et al. patent is extended or adjusted under 35 2004/0225,091 A1 11/2004 Lewandowski et al. U.S.C. 154(b) by 4 days. 2005/0065300 A1 3/2005 Lewandowski et al. 2005/0192370 A1* 9, 2005 Fansler et al. .................. 522f1 (21) Appl. No.: 11/868,793 2006/0074211 A1* 4/2006 Fansler et al. ..... ... 526,319 2006/O128825 A1 6/2006 Fansler et al. ............... 522,115 (22) Filed: Oct. 8, 2007 2006/0165999 A1* 7/2006 Fansler et al. ............ 428/411.1 (65) Prior Publication Data 2007/019 1564 A1* 8, 2007 Fansler et al. ............... 526,319 US 2008/OO27210 A1 Jan. 31, 2008 FOREIGN PATENT DOCUMENTS Related U.S. Application Data WO WO 96/30421 10, 1996 (62) Division of application No. 11/081,218, filed on Mar. WO WO97, 18247 5, 1997 16, 2005, now Pat. No. 7,294,742, which is a division WO WO99,31144 6, 1999 of application No. 10/316,334, filed on Dec. 11, 2002, WO WOO2,24761 A1 3, 2002 now Pat. No. 6,992,217. WO WOO2,26836 A2 4, 2002 WO WOO2,28914 A2 4/2002 (51) Int. Cl. WO WO 2004/052943 A1 6, 2004 C08G 69/26 (2006.01) WO WO 2004/052944 A1 6, 2004 (52) U.S. Cl. ....................... 528/332: 528/367:528/369; WO WO 2004/072127 A1 8, 2004 525/308: 525/314: 556/31556/110:556/136; WO WO 2004/072139 A1 8, 2004 556/138: 562/567; 562/574; 526/135; 526/146; 526/147; 526/204; 526/220; 526/307.1; 526/317.1: 526/318; 526/319; 560/70 (Continued) (58) Field of Classification Search ................. 528/332, 528/367, 369; 525/308,314: 556/31, 110, OTHER PUBLICATIONS 556/136, 138: 562/567,574; 526/135, 146, A. Sebenik “Living Free-Radical Block Copolymerization Using 526/147, 204, 220, 307.1, 317.1, 318, 319; Thio-Iniferters”. Prog. Polym. Sci., (1998), pp. 875-917, vol. 23. 560/70 “Polyazlactones'. Encyclopedia of Polymer Science and Engineer See application file for complete search history. ing, (1988), pp. 558-570, vol. 11, 2" Edition, John Wiley and Sons. K. Matyjaszewski et al., “Atom Transfer Radical Polymerization'. (56) References Cited Chemical Reviews, (2001), pp. 2921-2990, vol. 101, No. 9. U.S. PATENT DOCUMENTS (Continued) 4,304,705 A 12, 1981 Heilmann et al. 5,097,007 A 3, 1992 Himori Primary Examiner Ling-Siu Choi 5,314,962 A 5, 1994 Otsu et al. Assistant Examiner—Bijan Ahvazi 5,356,947 A 10, 1994 Ali et al. (74) Attorney, Agent, or Firm Kent S. Kokko 5,506,279 A * 4, 1996 Babu et al. .................... 522/34 5,527,921 A * 6/1996 Haubrich ................. 548,334.5 (57) ABSTRACT 5,763,548 A 6/1998 Matyjaszewski et al. 6,143,848 A 11/2000 Lee et al. 6,310,149 B1 10/2001 Haddleton Initiators for atom transfer radical polymerizations are 6,407,187 B1 6/2002 Matyjaszewski et al. described. The initiators have an azlactone or ring-opened 6,448,337 B1 * 9/2002 Gaddam et al. ............. 525, 193 aZlactone moiety to provide telechelic (co)polymers. 6,677,413 B1 1/2004 Lewandowski et al. 6,680,362 B1 1/2004 Fansler et al. 13 Claims, No Drawings US 7,557,177 B2 Page 2 FOREIGN PATENT DOCUMENTS Polymerization: The RAFT Process'. Macromolecules, (1999), pp. 2071-2074, vol. 32, American Chemical Society. WO WO 2004/094484 A1 11, 2004 WO WO 2004/0944.85 A1 11, 2004 M. Freemantle, “In Control of a Living Process”. Chemical and WO WO 2004/099275 A1 11, 2004 Engineering News, (Sep. 9, 2002), pp. 36-40. WO WO 2004/099276 A1 11, 2004 G. B. Fields et al., “Solid Phase Peptide Synthesis Utilizing 9-fluorenylmethoxycarbonyl Amino Acids”. International Journal of OTHER PUBLICATIONS Peptide & Protein Research, (1990), pp. 161-214, vol. 35. J.S. Wang, “Controlled “Living” Radical Polymerization, Halogen G. B. Fields et al., Chapter 3, “Principles and Practice of Solid-Phase Atom Transfer Radical Polymerization Promoted by a Cu(I)/Cu(II) Peptide Synthesis”. Synthetic Peptides: A User's Guide, G. A. Grant Redox Process', Macromolecules, (Nov. 6, 1995), pp. 7901-7910, Edition, (1992), pp. 77-183, W. H. Freeman and Co., New York, NY. vol. 28, No. 23. W. B. Lawson et al., “Modification of a Methionine Residue Near the S. M. Heilmann, "Chemistry and Technology of 2-Alkenyl Active Site of Chymotrypsin'. J. Am. Chem. Soc., (1962), pp. 2017 Azlactones”,Journal of Polymer Science: Part A: Polymer Chemis 2018, vol. 84. try, (2001), pp. 3655-3677, vol.39, John Wiley and Sons, Inc. Registry No. 151142-96-0, ACS on STN. (2005), p. 1. Y. K. (Bill) Chong, "A More Versatile Route to Block Copolymers and Other Polymers of Complex Architecture by Living Radical * cited by examiner US 7,557,177 B2 1. 2 RING-OPENED AZLACTONE NITIATORS trolled radical polymerization process which provides telech FORATOM TRANSFER RADICAL elic (co)polymers capable of entering into further POLYMERIZATION polymerization or functionalization through reactive end groups, particularly electrophilic end groups. This application is a divisional of U.S. Ser. No. 11/081,218, filed Mar. 16, 2005, now U.S. Pat. No. 7,294,742; which is a SUMMARY OF THE INVENTION divisional of U.S. Ser. No. 10/316,334, filed Dec. 11, 2002, now U.S. Pat. No. 6,992,217, the disclosures of which are The present invention provides initiators for atom transfer herein incorporated by reference. radical polymerization processes that comprise compounds 10 of the formula: FIELD OF THE INVENTION The present invention provides initiators and initiator sys tems for atom transfer radical polymerization (ATRP) pro CCSSCS. 15 BACKGROUND In conventional radical polymerization processes, the polymerization terminates when reactive intermediates are destroyed or rendered inactive; radical generation is essen tially irreversible. It is difficult to control the molecular wherein X is Cl, Br, or a pseudohalogen group; weight and the polydispersity (molecular weight distribution) RandR are eachindependently selected from X, H, an alkyl of polymers produced by conventional radical polymeriza group, a cycloalkyl group, a heterocyclic group, an arenyl tion, and difficult to achieve a highly uniform and well-de 25 group and an aryl group, or R' and R taken together with fined product. It is also often difficult to control radical poly the carbon to which they are attached form a carbocyclic merization processes with the degree of certainty necessary in ring: specialized applications, such as in the preparation of end R and R are each independently selected from an alkyl functional polymers, block copolymers, star (co)polymers, group, a cycloalkyl group, an aryl group, an arenyl group, and other novel topologies. 30 In a controlled radical polymerization process radicals are or RandR' taken together with the carbon to which they generated reversibly, and irreversible chain transfer and chain are attached form a carbocyclic ring; termination are absent. There are four major controlled radi Q is a linking group selected from a covalent bond, cal polymerization methodologies: atom transfer radical (—CH2—), CO-O-(CH2) , CO. O. polymerization (ATRP), reversible addition-fragmentation 35 (CHCHO). , —CO NR (CH) , —CO S chain transfer (RAFT), nitroxide-mediated polymerization (CH2). , where o is 1 to 12, and R is H, an alkyl group, (NMP) and iniferters, each method having advantages and a cycloalkyl group or an aryl group; and disadvantages. n is 0 or 1. Atom transfer radical polymerization (ATRP) has been The present invention also provides initiators that comprise described as a simple, versatile and efficient controlled radi 40 the ring-opened reaction product of the initiators of Formula cal polymerization process. See M. Freemantle, “In Control I and a reactive compound, Such as an aliphatic compound, of a Living Process”, Chemical and Engineering News, Sep. having one or more nucleophilic groups. Such initiators have 9, 2002, pp. 36-40, ATRP processes typically employ an alkyl the general formula: halide as an initiator and a transition metal complex as a 45 catalyst to produce a polymeric radical in the presence of a II OOC.
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